JPS5989696A - Novel plant protector, manufacture and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel phosphoric acid esters and agriculturally suitable salts, quaternary azolium and ammonium salts and metal complexes thereof having the following formula I: The present invention further relates to methods for producing these compounds and pest control agents as agricultural chemicals containing at least one of the novel compounds as an active ingredient. The invention also relates to a method for preparing such compounds and a method for controlling pests or for treating plants to prevent them from being attacked by pests.

Therefore, the present invention is based on the following formula: ■ (wherein, X represents a bridge member -0H= or -N=, Ar represents a phenyl group, diphenyl group, or naphthyl group, and %, R1, and bird each independently represents one of a hydrogen atom, a nitro group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a haloal-ON having 1 to 3 carbon atoms; a C2-C10 alkenyl group substituted by a halogen atom; an unsubstituted or C2-C10 alkynyl group substituted by a halogen atom; or a C3-C8 cycloalkyl group; substituted or substituted with a halogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, -ON or -OF; or a C2-alkyl group; can be interrupted by an oxygen or sulfur atom and is unsubstituted or a halogen atom, a phenyl group,
-000-C1-C4 argyl group, -〇〇-C1-C4 alkyl group, -Co-phenyl group, unsaturated or saturated 5 containing oxygen or sulfur atoms as non-carbon atoms - or a carbon atom substituted by an atom or group selected from the group consisting of a 6-membered ring and in which each phenyl moiety is unsubstituted or substituted by one or more of the same or different halogen atoms. represents an alkyl chain having a number of 1 to 12 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, each unsubstituted, or a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
an alkyl group, an alkoxy group having 1 to 4 carbon atoms,
-ON or -OF, represents a Fe, Nyl group or a benzyl group substituted by, and Bird and Horse each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, t- having 3 carbon atoms, 7 cycloalkyl group, or aromatic ring is unsubstituted or halogen atom, alkyl group having 1 to 4 carbon atoms, 1 carbon atom
represents a phenyl group or benzyl group substituted with -ON or 10F, or a 6-membered alkoxy group, or a 6-membered forms a saturated or unsaturated heterocyclic ring, and Ro and Ro each independently represent a hydrogen atom, a C1-C40 alkyl group or an unsubstituted or halogen atom, a C1-C4 alkyl group, -ON or -OF, horse. represents an alkyl group having 1 to 12 carbon atoms, and RQl represents -YR12 to an alkyl group having 1 to 12 carbon atoms or a phenyl group.

H represents a C1-C12 alkyl group <1, and Y represents an oxygen atom or a sulfur atom. ), as well as scattered salts, quaternary azolium and ammonium salts, and metal complexes thereof.

Alkyl groups with a specified order of carbon atoms, by themselves or as part of other substituents, include, for example, the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl. , octyl group, nonyl group, decyl group, undecyl group, or dodecyl group, and isomers thereof, such as isopropyl group, isobutyl group, tert-butyl group, impentyl group, and the like. Alkenyl groups are, for example, vinyl, propen-1-yl, allyl, butene-1-
yl group, buten-2-yl group, buten-3-yl group, etc.
as well as chains containing several double bonds. Examples of the alkynyl group include a propyn-1-yl group, a propargyl group, a buten-1-yl group, a butyn-2-yl group, and a propargyl group is preferred. C, S2 Tetraalkyl groups are particularly suitable for monohalide to perhalogenated alkyl substituents such as 0HOH1,OH,01゜00&
, OFs, O)(*0H4CI, etc. Throughout this specification, a halogen atom means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a chlorine atom, a bromine atom, or a fluorine atom is preferable.The cycloalkyl group is, for example, Cyclopropyl group, cyclobutyl group, cyclopentyl group,
It is a cyclohexyl group type or a cycloheptyl group, and cyclopropyl and cyclohexyl groups are preferable.

Heroalkenyl radicals are alkenyl radicals substituted by one or more halogen atoms, such as chlorine and bromine atoms, especially chlorine atoms. The furyl group is preferably a 2-furyl group, a tetrahydrofuryl group, preferably a 2-furyl group.
-tetrahydrofuryl group. Among the pyridyl groups, a pyrid-3-yl group or a pyrid-4-yl group is preferred.

The naphthyl group is an α- or β-naphthyl group, and an α-naphthyl group is preferred. Examples of 5- or 6-membered heterocycles containing up to 3 nitrogen atoms are pyrazole, imidazole,
i, 2.4-) lyazole and t3.4-triazole, pyridine, pyrazine, pyrimidine, pyridazine, L&
5-) riazine and 1,2.4-) riazine.

Examples of salt-forming acids are inorganic acids, such as hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid; also sulfuric, phosphoric, phosphorous, nitric acids; and organic acids. Acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, tartaric acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluene Sulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid.

Metal complexes of the formula I are composed of basic organic molecules and inorganic or organic metal salts, such as elements from main groups 3 and 4 of the periodic table, such as aluminum, tin or lead, and elements from subgroups 1 to 8, such as chromium. , halides, nitrates of manganese, iron, cobalt, nickel, copper, zinc, silver, mercury, etc.
These include sulfates, phosphates, acetates, trifluoroacetates, trichloracetates, propionates, tartrates, sulfonates, salicylates, benzoates, and the like. Preferred elements are those of the quaternary female family. Metals can exist in different valence states. The metal complex of formula I may be monocyclic or polycyclic.

That is, they can be used alone as ligands or compounds of formula I are stable oils, resins or primarily solids at room temperature and have very valuable microbial control properties. They can be used prophylactically or therapeutically in agriculture and related fields to control pests such as molds, insects and mites, and for their efficacy the formula 1
Triazolylmethyl derivatives within the range (X represents N) are preferred. Cultivated plants are highly tolerant of compounds of formula I. The growth of the plant is not hindered or delayed at any stage;

An important and preferred subgroup of compounds of formula I is the following formula i": (wherein X represents the bridge member -0H= or -N= and represents phenyl, diphenyl or naphthyl group, R,, R1 and horse each independently represent a hydrogen atom, a nitro group,
Halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms or 1 carbon atom
represents an alkyl group having 1 to 3 carbon atoms; 36 phenyl group, each substituted with one or more nitro groups, halogen atoms and/or methyl groups; or benzyl group, horse. represents an alkyl group having 1 to 6 carbon atoms, and ru represents -YI%t, an alkyl group having 1 to 6 carbon atoms or a phenyl group.

R represents an alkyl group having 1 to 6 carbon atoms, and Y represents an oxygen atom or a sulfur atom. ) and agriculturally suitable salts, quaternary azolium and ammonium salts, and metal complexes thereof.

A more preferred subgroup is represented by the formula 1, in which X represents a bridge member -0H= or -N=; Ar represents a phenyl group; the ortho-position represents a hydrogen atom, a nitro group, a halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, 1 to 3 carbon atoms
represents a haloalkyl group: the para position represents a hydrogen atom, a nitro group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms; Representation: Horse represents a hydrogen atom, methyl group or halogen atom, R represents a group -
000R,.

R4 represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a phenyl group or benzyl group each substituted with one or more nitro groups, halogen atoms and/or methyl groups; or 1
0 alkyl groups or each unsubstituted or halogen atom, C 1 -C 4 alkyl group, C 1
represents a phenyl group or benzyl group substituted with -ON or -OF;
each of horse and horse independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a phenyl group or a benzyl group; R1° is 1 to 4 carbon atoms; represents an alkyl group; R,,
-YR, , represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; 也 represents an alkyl group having 1 to 4 carbon atoms; and a compound in which Y represents an oxygen atom or a sulfur atom; , quaternary azolium and ammonium salts and metal complexes thereof.

Hereinafter, this subgroup will be referred to as compound I.

Another particularly preferred subgroup is represented by formula I, in which X represents a bridge member -N=;
or a phenyl group substituted at the para position with a nitro group, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group and/or an OF; each represents a nitro group, a salt, a phenyl group or a benzyl group substituted with a atomic atom, a bromine atom, a fluorine atom and/or a methyl group;
Gift. represents an alkyl group having 1 to 4 carbon atoms) t)
L/; a compound in which R11 represents -YRtt, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and Nyl represents an alkyl group having 1 to 4 carbon atoms; and Y represents an oxygen atom or a sulfur atom; Splurge on salt,
Included are quaternary azolium and ammonium salts and metal complexes thereof.

The following individual compounds are particularly preferred microbial control agents: ■■, H3 ·'10 Formula! The compound represented by the following formula (1): An alcohol represented by the following formula (2) is combined with a phosphoryl halide represented by the following formula (2), preferably in the presence of an inorganic or especially an organic base, from -20' to +15%.
The reaction is carried out in the temperature range of 0° C., preferably in the range of 0 to 100° C., and in the absence of solvent or in the presence of an inert organic solvent or diluent and/or the free compound obtained in this step is subjected to sprinkling salting. or converting into a quaternary azolium salt or ammonium salt, or converting the dispersion salt or quaternary azoliuf salt or ammonium salt obtained by this step into the free compound or other dispersion salt, quaternary azolium or ammonium salt. or by converting the free compounds or salts obtained by the process of the invention into metal complexes. Substituents R9 bird, bird, bird, R4, horse 0. Horse 0. Y.

X and Ar have the same meanings as defined in formula 1, and Hal in formula 1 is a halogen atom.

Preferably it represents a chlorine atom or a bromine atom.

Examples of suitable solvents for the reaction are aliphatic and aromatic hydrocarbons,
For example benzene, toluene, xylene, petroleum ether:
Halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, ethylene chloride; ethers and ethereal compounds, such as evadialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.). ), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; N,N-dialkylated amides such as dimethylformamide; dimethyl sulfoxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone; A mixture of. It is often advantageous to carry out the reaction or some stages of the reaction in an inert gas atmosphere and/or in an anhydrous solvent.

Suitable inert gases include, for example, nitrogen, helium, argon, and optionally carbon dioxide. The yield can also be improved by conducting the reaction at high temperatures.

Examples of suitable inorganic salts are the oxides, hydrides, hydroxides, carbonates, carboxylates and alcoholates of alkaline earth metals, preferably alkali metals, especially the sodium and potassium salts (e.g. NaH, NaOH, KOH, Na1OOB, @00B
, 0aOO3゜OH, 00ONa, 02H@0OOK
, 0tHsONa, OI (, ONa, etc.), preferably an alkali metal hydride such as NaH. Suitable organic bases are trialkylamines such as triethylamine or other tertiary amines such as triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine, and the like.

The intermediates and final products obtained by the production process of the invention can be separated from the reaction solvent and, if freshly pickled, by one of the commonly used methods, such as extraction, crystallization, chromatography, distillation, etc. Can be purified. Particularly advantageous variants of the process for obtaining the compounds of the formula (1) and the intermediates, in particular the intermediates of the formula (2), are illustrated in two reaction mechanisms and are subsequently explained in detail.

Formula 1a YoQ Ib, I, I, IV, V, V
I, W, Vl, ■, X.

n, m, xu and up to ■ substituents rtXt
R, melon, bird, bird, tori, bird, bird, to, R1, turtle. , melon, and Y have the same meanings as defined in Formula I.

In formula xv, Q is a conventional leaving group, such as a halogen atom, preferably a chlorine, bromine, or iodine atom, or a sulfonyloxy group, preferably tt, < is a benzenesulfonyloxy group, a p-tosyloxy group, or a lower alkylsulfonyl group. It represents either an oxy group, preferably a mesyloxy group; or an acyloxy group such as a trifluoroacetyloxy group.

Q can also be a hydroxyl group or °synthesis.
is)' 1979, pages 561 to 569, represents a group represented by the following formula: (wherein and 4 represent an organyl group, preferably a lower alkyl group or an unsubstituted or substituted alkyl group). M represents a hydrogen atom or a metal atom, preferably an alkali metal atom, most preferably sodium or potassium.

Hal represents a halogen atom, preferably a chlorine atom or a bromine atom. Y represents a halogen atom, preferably a chlorine atom or a bromine atom, or a sulfuric acid ester group or a sulfonic acid ester group. has the same meaning as defined.) means a group represented by

Person 2 means the following azoyl group: (wherein X represents 10H= or -N=).

,.17 is the reaction mechanism (1) 1311-4.18 /19 The method for producing the compound represented by the formula (2) and its intermediates will be described in detail below.

1) Free α-hydroxycarboxylic acid represented by formula (■) can be obtained by hydrolyzing either dioxolanone represented by formula (2) by 2A or cyanohydrin represented by formula (2) by 2B in a base or acid medium. built.

Hydrolyzed anti-meijin and B are acids or bases, aqueous and/or
or advantageously carried out in an alcoholic solution, ie a polar solvent. The reaction can also be carried out in a two-phase medium, in which case it is advantageous to add customary phase transfer catalysts.

Inorganic or organic acids are suitable, e.g. hydrohalic acid,
Examples include mineral acids such as sulfuric acid and phosphoric acid, or sulfonic acids (<p-toluenesulfonic acid, methanesulfonic acid). Suitable bases are organic and inorganic bases, such as oxides, hydrides, hydroxides, carbonates of alkaline earth metals and alkali metals.

carboxylates and alcoholates, especially the above compounds of sodium and potassium.

The reaction temperature for the ring-opening reaction of 2A is generally from 08° to +140°C, preferably from +30° to +80°C, and the temperature for the hydrolysis of cyanohydrin I is from +60°C.
° to +140°C, preferably +80° to +1
20° C., or for both reactions at the boiling point of the solvent or solvent mixture.

Many of the starting compounds of formula (1) are known from European Patent Specification No. 3aa2y6. The new compounds can be made by methods corresponding to those described in the patent specification.

The nitrile ■ (variant B) can be prepared from the following formula ■: from the -ruazolyl methyl ketone to HO
N or alkali cyanides such as KON or Na0
N and, at 0° to 100° C., advantageously trace amounts of base (
Preferably in the presence of NH, OH or ammonia gas, by the method of cyanohydrin synthesis, or by the formula
Corresponding NaH3O, adduct method for the compound [Organic Synthesis Collection (Org,
5ynthesesOo11. ) J Volume 1, No. 33
6 pages or French patent specification tube 2,292,706
No. 2 year old girl Houben Weyl
) Author:
Methoden der Organischen O
hemie)” Vol. 6/3, p. 412].

Nitrile■ is also featured in the Journal of Organic
Compound 1 was reacted with trimethylsilyl cyanide in the presence of a catalytic amount of Zn Is, followed by hydrolysis of the adduct, according to Chemistry (J, Org, Ohem, ) Vol. 59, p. 914 (1974). It can be created by doing.

These nitrites can also be used advantageously in an inert solvent with ketones and di-lower alkylcyanohydrins of the formula % (wherein "alkyl" preferably represents a methyl, ethyl or propyl group). Alternatively, it can also be produced by reacting at a temperature of 50° to 150°C without a solvent.

The hydrolysis of IJL (2) to the acid derivative represented by the formula (2) can be carried out by a method similar to the known method using concentrated hydrochloric acid (Houben-Peil, "Metho-Demper Organidiene Hemi- ”, Volume ■No. 42
(See pages 7 onwards).

Some of the ketones of the formula (1) used above the intermediates are known from DE 2451407 or British Patent Specification No. 14t54224. Ketones of this type are also known as (53) Corresponding ketals, for example in the following documents: DE-OS 2610022, DE 2602770, DE 2602770, 29!
No. 10029, No. 2930196 and No. 294013
It can also be obtained by hydrolysis from those described in any of No. 3.

The ketone represented by the formula ■ is not listed.

It can be obtained by one of the methods described in the above-mentioned documents.

;)4 11) The compound represented by formula ■ is
In the usual manner, the corresponding acid derivative ■ (also in the form of its alkali metal salt) is prepared with the formula Xv:Rs-Q' (
XV) It can be produced by esterifying the compound represented by: -20° to +40°C. Neutral solvents are preferred for this reaction. Direct esterification is carried out with excess alcohol R5-OH at 0° to 80°C.
It is advantageously carried out in the presence of a mineral acid or preferably a Lewis acid such as poron trifluoride etherate.

The compound represented by formula (2) can also be formed by combining a-haloacetate of formula (1) and paraformaldehyde at 20°
at a temperature of from 40° to 140°C, preferably from 40° to 80°C,
and a) preparing the desired azole of formula (i.e. imidazole or triazole) in the presence of a base (e.g. NaOH) or an alkali metal salt of the azole of formula (i) in an anhydrous solvent (e.g. dimethyl sulfoxide). I can do it. The .alpha.-haloacetate of formula (1) can be obtained by conventional esterification of the corresponding known acid MV.

The ester represented by the formula ■ can also be expressed by the formula
oxirane and azole K (M represents It or an alkali metal) in an inert solvent, preferably a polar solvent (DM
F, acetonitrile, DMSO, etc. or mixtures thereof with hydrocarbons) at 20° to 100°C. Inorganic or organic bases can be added to this reaction (see EP 15756). As shown in the reaction scheme, the oxirane represented by formula
OH, peracetic acid). Compounds of formula X are prepared from aryl acetates of formula x by reaction with oxalates of formula
caActa) Vol. 30, p. 1349).

Esters of formula ■ can also be prepared by preparing an acid of formula ■ with a dimethylformamide acetal (preferably in excess), the acetal component of which is intended to form the alcohol portion of the ester, in a solvent such as a similar absolute alcohol or ether) at 0° to 160°C.
Angew-Chemie Vol. 75, p. 296 (1963) and Helvetica Chimica Acta Vol. 48, p. 1747 (1965)).

-) The thioester of the formula Lf in the second reaction scheme can be prepared from the acid and the thioalcohol in the presence of a weak base (tertiary amine) in a neutral solvent such as CHCl, DMF, dichloromethane, DMSO. -10° to +120
It can be obtained at a temperature of preferably Do to +40°C. These compounds are reacted with the subsequent phosphoryl halide (1) to obtain a compound represented by formula 1c. 1 g of corresponding mandelic acid amide and mandelic acid hydrazide
is the ester (t or thioester) of formula If and excess amine R? -NH-R8. Mandelic acid amide and hydrazide Ig are reacted with their successor compound (2) to obtain a compound represented by formula 1d. R6 and R7
When is closed to form a 5t or 6-membered ring, as in the case of compounds of formula 1e, such heterocycles are formed by converting the acid 1 with a 1,1'-carbonyl diazole or diazine,
It can advantageously be introduced by reaction at temperatures between 0° and 150° C., preferably in a solvent such as an ether or a halogenated hydrocarbon. The obtained compound represented by formula th is reacted with the phosphoryl halide of its successor (①) to obtain a compound represented by formula Ie.

lv) The free hydroxyl groups of compounds (1) and Tanaka are phosphorylated with the phosphoryl halide represented by (2) as described above.

:]8 All variants mentioned under 1), ill, m) and +V) constitute the object of the invention.

Other formulas m, IX, X11. The starting compounds of xm and XV are known or can be obtained by methods known per se.

The compound of the following formula 1: contains an asymmetric center adjacent to the aromatic groups Ar and R and can therefore be obtained in the form of two optical antipodes. Generally, the processes for preparing these compounds result in mixtures of the two optical antipodes. This mixture can be separated into the optical antipodes in a conventional manner. The optically pure enantiomer can be obtained, for example, by converting an optically pure a-hydroxycarboxylic acid of the formula ■ into an optically pure compound of the formula ■ according to variant C; can be obtained by phosphorylation to give a compound of formula 1a as described in Variant F, and this compound is reacted to further convert it into a compound of formula I. a- expressed by the optically pure formula ■
Hydroxycarboxylic acids can be obtained, for example, by reacting grape acid (1) with an optically pure base and by fractional crystallization.

Unless otherwise specified, for compounds represented by formula ■,
A mixture of the two optical enantiomers shall always be meant. The two optical antipodes have different microbicidal properties.

Surprisingly, it has been found that the compound 2 has a fungicidal spectrum that is very useful against phytopathogenic fungi and bacteria in practice.

They have very effective curative, systemic and prophylactic properties and can be used for the protection of many cultivated plants. When using the compounds of formula I, it is possible to inhibit or destroy microorganisms occurring on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) in useful plants for food, while at the same time Subsequently growing parts of the plant are also protected from damage by microorganisms.

The compounds of formula ■ are active against phytopathogenic fungi belonging to the following classes: Cystomycetes [e.g.
turia), Podosphaera
era), Erysiphe x, Mon111nia, Uncinula (U
ncinula): Basidiomycetes [e.g. genera Hemileia, Rhizoctonia, Pe
llicularia), Puccini
a ) ) ; Deuteromycetes [e.g. Botrytis (Bot.
rytis), Helmintosporium (He 1mi)
nthosporium), Fusariu A (Fu
sarium), Cebutria (5eptoria)
, Cer-cospora, Piricularia and Alternaria) & Pythium (P
ythium).

formula! The compound represented by
It is also effective against Xanthomonas species of the family. Furthermore, the compounds of formula I have a systemic action (51). They can also be used as a dusting agent to protect seeds (fruits, tubers, grains) and cuttings from fungal infections and from phytopathogenic microorganisms occurring in the soil. .

The compounds of the invention also have a particularly low effect on plants. The remarkable action against rust fungi in cereals and rice varieties is particularly noteworthy.

The compounds of formula (II) are also suitable for controlling animal and plant pests and pests in soil.

Therefore, the compound represented by the formula
Lepidoptera), Coleoptera
ra), Homoptera, Heteroptera (
Heteropte'ra), Diptera
), Thysanoptera, Orthoptera, Anoptera
ura), Siphonaptera, Mallophaga, Thys
anura), Isoptera L-Psocoptera, and Hymenoptera and Aca
Suitable for controlling mites and ticks of the order (Rina).

(;2 In particular, the compound represented by the formula ! is suitable for controlling plant-damaging insects, especially plant-feeding pests, in cultivation areas of ornamental plants and useful plants, and is particularly suitable for controlling plant-damaging insects, especially plant-eating insects, such as Spodoptera littoralis.
oralis) and Helios bivtuscens (He
liothis virescens), insects that attach to vegetables such as Colorado potato beetles (Leptin
otarsa decemlineata) and green peach aphid (Myzus persical).

It should be emphasized in this connection that the compounds are effective against sucking insects and especially against the family Aphidae, which is very difficult to control by known pest control agents.
It has both a very pronounced osmotic and tactile action against insects such as Aphis fabae, Apis craecivora and Myzua persicae. .

The active ingredients of the formula I also have a very effective action against flies, such as the house fly (Musca domestica) and against mosquito larvae.Furthermore, the compounds of the formula I have a wide range of It has ovicidal and ovicidal larvicidal effects on ectoparasitic mites and ticks, such as Iginidae (I
xodidae)-, Argasidae
e) - and Dermany-ssi
It has a useful action against mites of the dae family.

The present invention therefore provides fungicidal compositions and compounds of the formula - for the control of agricultural pests, in particular fungi and insects that damage plants, and for preventive treatments to protect plants from attack by such pests. or more compounds or groups of compounds. The invention further relates to a method for treating plants, characterized in that the method comprises applying to the plants a compound of formula (1) or a novel composition.

Target crops protected within the scope of the invention include the following plant species: cereals (wheat, barley, rye, oats, rice, sugar corn and related crops), beets (sugar beets and fodder beets), stone fruits. , pear fruit and soft fruit (#) apple,
Pears, plums, peaches, almonds, cherry blossoms, strawberries, raspberries and plum berries), legumes (fava beans, lentils, peas, soybeans), oil plants (oil, mustard, hobby, olive, sun) Flowers, coconut, castor oil, cocoa beans, peanuts), Cucurbitaceae (cucumbers, marrows, melons), 1iUl products (M, flax, hemp, jute), species plants (
orange, lemon, grapefruit, mandarin),
Vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, bell peppers, paprika)
, Lauraceae (avocado, cinnamon, camphor), or corn, tobacco, nuts, coffee, sucrose, tea,
Grape vines, hops, (j5 banana and natural rubber plants, and ornamental plants.

The compounds of formula I are usually applied in the form of compositions and may be applied simultaneously or sequentially with other compounds to the crop ground or to the plants to be treated. These other compounds may also be fertilizers and/or micronutrient providers or other formulations that influence plant growth. Selective herbicides, insecticides, fungicides, bactericides, nematode eradicators, if desired, together with carriers, surfactants or application promoting aids conventionally used in the pharmaceutical industry. , molluscicides or mixtures of some of these preparations. Suitable carriers and auxiliaries can be solid or liquid and include substances commonly used in formulation technology, such as natural or recycled minerals, solvents,
It corresponds to a dispersant, a wetting agent, an adhesive, a binder or a disinfectant.

The compounds of formula 1 are used in neat form or, preferably with auxiliaries customary in the pharmaceutical industry, and are prepared in known manner as emulsion stock solutions, coatable pastes, etc.
aste), directly sprayable or dilutable solutions, dilute emulsions, aqueous solutions, aqueous solutions, powders, granules, and encapsulates, for example with polymeric substances. As well as the nature of the composition, spraying, atomization,
Application methods such as dusting, sprinkling or pouring are chosen depending on the intended target and the environment of use. Advantageous application rates are usually from 50 to 5 Kg of active ingredient (a,t) per hectare, preferably from 100 F to 2 Ky a,
i/ha, most preferably 20 OP to 600
y a, i, /ha.

Preparations, i.e. compositions or formulations containing a compound of formula (active ingredient) and, where appropriate, solid or liquid auxiliaries, may be prepared by known methods, for example, by combining the active ingredient with a solvent, solid carrier and, where appropriate. are prepared by homogeneously mixing and/or milling with a bulking agent such as a surface-active compound C (surfactant).

Suitable solvents are: aromatic hydrocarbons, preferably C8-C12 moieties, such as xylene mixtures or substituted naphthalenes; phthalates such as diptylphthalate or dioctyl phthalate; cyclohexane or paraffin. Aliphatic hydrocarbon; ethanol,
Alcohols and glycols and their ethers and esters such as ethylene glycol monomethyl or monoethyl ether; more ketones of cyclohexanone; strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide; and epoxidized coconut oil or an epoxidized vegetable oil such as soybean oil; or water. Solid carriers which can be used, for example in dusts and dispersible powders, are usually natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite, highly dispersed silicic acids or It is a highly dispersed absorbent polymer.

Suitable granulated absorbent carriers are of porous type, such as pumice, crushed brick, sepiolite or bentonite; and suitable non-absorbent carriers are calcite or dolomite. Ground plant residues can also be used. Phospholipids can also be used with particular advantage.

Depending on the nature of the compound of formula i to be formulated, suitable surfactants are nonionic, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties. It is to be understood that the term "surfactant" also includes mixtures of surfactants.

Surfactants customary in the pharmaceutical industry are, for example, those described in the publication No. 1 McCutchan's Detergents and Emulsifiers Annual (Me
tcheon's Detergents and Em
Mac Publishers, Ringwood, New Chassis, 1981.

and H-5tache,
”Ten5id-T
asche-nbuch)”, Karl Hanser (Ca.
Hanser)-Publisher, Munich/Vienna 1981° Pesticide formulations usually contain 0.1 to 99% of the compound of 2, preferably α1 to 95%, solid or liquid adjuvants 1 to 99.9%, preferably 99.9%. 8 (59% to 5%) and surfactant % to 25%, preferably 0.1 to 25%.

Although commercial products are preferably formulated as concentrates, consumers typically use dilute formulations.

The compositions may also contain other ingredients such as stabilizers, defoamers, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients for special effects.

EXAMPLES The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, parts and parts indicate weight parts and weight %.

Production Example Example P1 Formula: 2-(IH-1,2,4-triazolylmethyl-1'-yl)-2-(2-chloro-4-furomophenyl)-2-ethoxycarbonyltetrahydrofuran 701 15jll (0,
04 mol) t-containing solution in tetrahydrofuran 50a
Sodium hydride 55% in paraffin oil in l
It is added dropwise to a suspension containing 1.89 (α04 mol) of the dispersion at room temperature. After 2 hours, the evolution of hydrogen was completed, and then diethyl chlorophosphate was added to 70 al of tetrahydrofuran.
) 8.37 (0,048 mol) is added dropwise at room temperature and the reaction mixture is stirred overnight at the same temperature. The mixture is then stirred for a further 16 hours at a bath temperature of 80° C. and subsequently cooled to room temperature. The solvent is removed in a water jet vacuum, the residue is dissolved in ethyl acetate and the solution is washed with water. The ethyl acetate solution is dried over sodium sulfate, filtered, and the P solution is concentrated in a water jet vacuum. The crude product is purified by chromatography through silica gel with diethyl ether and increasing ethanol increments.

A yellow oil 4F with a refractive index n% = 1.5245 is obtained.

Example P2 Formula: Ethyl 2-(IH-1,2,4-)riazolylmethyl-1'-yl)-2-(2-chloro-4-bromophenyl)-2-ethoxycarbonyl-2-phosphate Preparation of n-propyl thioester Diethyl 2-(IH
-1,2,4-)riazolylmethyl-1'-yl)-2
-Hydroxy-2-chloro-4-bromoacetate-hl
A solution containing A15F ((1035 mol)) was added to 1.5 y of a 55% dispersion of sodium hydride in paraffin oil.
(α035 mol) dropwise at room temperature. After hydrogen evolution has stopped, the corresponding phosphoric acid ester chloride 7,89 (α038
mol) is added dropwise at about 10° to 15° C. and the reaction mixture is then stirred overnight at room temperature. The mixture is concentrated by water jet vacuum and the residue is then dissolved in ethyl acetate. The solution is washed with water, dried over sodium sulfate and then concentrated by water jet vacuum. Remove the shibara fin oil by dissolving the residue in acetonitrile and then washing the solution with petroleum ether. After separating both phases in a separatory funnel, the acetonitrile is removed by water jet vacuum. yield:
Oil 1[L5jE0 Example P3 with refractive index nD=1.5359 2-(IH-1,2,4-triazolylmethyl-1'-yl)-2-(2-chloro- A 55% dispersion α9p ([102 mol) of ethyl n-propyldithioester sodium hydride in 4-bromophenyl)-2-ethoxycarbonyl-2-phosphate was dissolved in tetrahydrofuran 2
7.551 ((102 mol) of the corresponding hydroxy compound in 50 d of tetrahydrofuran.
Add the solution containing at room temperature. Hydrogen generation ceases after 2 hours. A solution containing 4.8 p (Q, 022 mol) of the corresponding chlorothiophosphate in tetrahydrofuran 1105c is then added dropwise at 10° to 20°C, and the reaction mixture is stirred overnight at room temperature, then by water jet vacuum at 4°C. Concentrate. The residue is taken up in ethyl acetate, the solution is then washed with water, dried over sodium sulfate, FJ and the p solution is concentrated by water jet vacuum.

The freshly obtained residue is suspended in a small amount of acetonitrile, the suspension is then filtered and the furnace mass is washed with petroleum ether.

Yield: 6.6y0 of the title compound with a melting point of 100° to 112° C. The following compounds can be prepared according to the examples given above and variations described earlier in the text.

1 (J9 JiO Formulation example Formulation example of the active ingredient represented by formula 1 (all percentages are by weight) A) Emulsion stock solution a) b) c) Compounds in Tables 1 to 4 254 An 50g Calcium dodecylbenzenesulfonate 5 Regret Section 8 6
Castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 hours --Tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) -12 hours a#
I Cyclohexanone -15q62Q Excessive xylereno compound 65#) 254 20 By diluting the stock solution of baby formula with water, an emulsion with a desired concentration can be produced O B) Solution a) b) c) d) Table 1 -4 active ingredients 8011 101% 54
9511 Ethylene glycol monomethyl ether Part 20 ---Polyethylene glycol jLOo -70% --N-Methyl-2-pyrrolidone --Part 20 --Epoxidized coconut oil --1% 5% Petroleum distillate (boiling point range 160-190 C) - Qa - These solutions are suitable for application in the form of microdroplets O C) Granules a) b) Active ingredients from Tables 1 to 4 Part 5 10elb Kaolin 94% - Highly dispersed silicic acid
1% - attapulgite
- Dissolving 90% of the active ingredient in methylene chloride, spraying this solution onto the carrier and subsequently removing the solvent in vacuo D) Powders a) b) Active ingredients from Tables 1 to 4 Acid 1 t 5 talc
97chi -Kaolin-
By uniformly mixing the 90 active ingredient and the carrier,
By using it as it is, Rokuru powder can be obtained.

E) Irrigation agent a) b) c) Active ingredients from Tables 1 to 4 25% sol 75
% Sodium Lignosulfonate 54 51
- Sodium lauryl sulfate 3% - 5% Sodium diisobutylnaphthalene sulfonate - 6qb 10 tons Octylphenol polyethylene glycol ether (7 to 8 moles of ethylene oxide) - Part 2 - Highly dispersed silicic acid Part 5 10 10 Thikaolin
62% Section 27 --13 An irrigation agent that can be diluted with water to obtain a suspension of the desired concentration by thoroughly mixing the active ingredient with an auxiliary agent and then thoroughly grinding the mixture in a suitable mill. is obtained.

Biological test example ■, Action against plant pathogens a) Residual protection effect Wheat plants were treated with active ingredients (o, o6<) 6 days after sowing.
treatment with a spray mixture prepared from a wettable powder. After 2 A hours, the treated plants are infected with a suspension of fungal diaspores. This plant body has a relative soaking degree of 95 to 100,
Incubate for 48 hours at about 20°C and then leave in a greenhouse at about 22°C. The spread of analgesic warts is evaluated 12 days after infection.

b) Spraying mixture prepared from irrigating agents containing active ingredients 5 days after sowing the osmotic wheat plants (active ingredients o, oo based on the volume of soil)
6%), the treated plants are infected with fungi using a suspension of fungal diaspores. The relative temperature of the plant body is 95
~100%, incubated at about 20°C for 68 hours, then placed in a greenhouse at about 22°C. The spread of analgesic warts is evaluated 12 days after infection.

Untreated control plants infected with the fungus were attacked by 100%; plants treated with a composition containing a compound of formula I were only slightly attacked (<20°) or not at all. I was attacked. Compound 1.1, 1.
3, 1.19, 1.22.

1.65 and others completely prevented attack by bacteria (mouth to 5 sections).

Example B2: Cercospora arachidicola in peanuts
a) Residual protective effect on groundnut plants with a height of 10 to 15 tM with a spray mixture prepared from an irrigation agent of the test compound (active ingredient (100 tM)
2%), and 48 hours later, the fungi are infected with a conidial suspension of the fungi. The infected plants are incubated at about 21°C under high humidity for 72 hours and left in a greenhouse until typical spots appear on the leaves. After 12 days of infection, bactericidal activity is evaluated based on the number and size of spots.

b) Spraying the spray mixture prepared from the watering agent of the test compound (0.06% of active ingredient based on the volume of soil) on groundnut plants with a height of 10 to 15 crn. After 8 hours of OA, the treated plants were sprayed. Fungal conidia 11! I! Bacteria are infected with the suspension and cultured for 72 hours at approximately 21° C. under high turbidity.

The plants are then left in a greenhouse and fungal attack is evaluated 11 days after infection. Compared to control plants that were untreated and infected with fungi (number and size of spots = 100%), the incidence of Cercospora disease was significantly reduced in plants treated with the compounds in Tables 1 to 4◎ In the test of compound 1.1,1.3゜1.19
, 1.22, 1.65 and others almost completely inhibited the spread of speckles (from mouth to 10) and 90 cases B3: Erysiphe graminis on barley. a) Residual protective effect A spray mixture prepared from a test compound formulated as an irrigation agent (with 0 active ingredients) on barley plants with a high formula of approximately 86n
．． 0.3 to 4 hours after spraying with 0.02%), the treated plants are covered with conidia of the fungus. The infected barley plants are then left in a greenhouse at approximately 22°C. The degree of infection is assessed after 10 days.

b) Osmosis Treatment of barley plants with a height of approximately 8-8 cm with a spray mixture (active ingredient αoo 6 qb per soil volume) prepared from the test compound formulated in a hydrating powder. Be careful not to touch the plant parts. After 4 hours, the treated plants j-↓7 are infected with a suspension of fungal conidia. Barley plants infected with the fungus are left in a greenhouse at about 22°C, and the degree of infection is evaluated after 10 days.

The compounds of formula I and the compounds of Tables 1 to 4 suppressed fungal attack to less than 20%, while untreated and infected control plants were attacked by 100%. Compound 1.1, 1.
3, 1.19, 1.22.

1.65 and others completely reduced the fungal attack (to 5 degrees).

Example B4: Penturia inaquaris (
Venturia 1naequalis
) Apple cuttings with new shoots 10 to 20 efn in length are sprayed with a spray mixture prepared from the watering agent of the test compound together with a conidial suspension of the fungus.The plants are then exposed to a relative humidity of 90 Incubate for 5 days at ~100 cells, then incubate for another 10 days 2
Leave in a greenhouse at 0 to 24°C. Evaluate face skin infestation - L 8 after 15 days of infection. Compounds 1.3, 1.19, 1.22 and others prevent attacks below 104, some (e.g. compound 1.3)
completely prevented infection. In field tests, apple shoots were not hindered in growth and maintained their legs in the same way.Example B5: Residual protective effect against Botrytis cinerea (botrytis cinerea) in kidney beans. French bean plants are sprayed with a spray mixture (concentration o, 02 t) prepared from the test compound formulated as an irrigation agent. After 48 hours, the treated plants were infected with the fungus using a suspension of fungal conidia.
Incubate for 3 days at 1°C and then evaluate fungal attack. Many of the compounds in Tables 1 to 4 inhibited fungal attack very strongly. For example, compounds 1.1, 1.3° 1.19, 1.22 and 1.65 are very effective at a concentration of 0.02% (
Example B6: Piri-cularia oryzae in rice
After two weeks of cultivation, the rice plants were sprayed with a spray mixture (Part 0.02) prepared from the hydrated formulation of the test compound. Infect the live spore suspension with the fungus at relative humidity of 95-100 degrees and 24°C.
After 5 days of incubation, bacterial attack is evaluated. Compared to a 100% attack on unprotected plants, the compounds of Tables 1 to 4, compound 1.1 and others, sufficiently prevent fungal infection. Compound 1.51 completely inhibited bacterial attack even when diluted to a concentration of 0.00296
Example B7 of action against harmful microorganisms: Aedes aegypti K
By dispensing a predetermined amount of a 0.1 acetone solution of each of the compounds to be tested on the surface of 150 tnl of water placed in each of a number of beakers, each of 800 and AOO
After evaporation of the acetone, the active ingredient plkIf of ppm is obtained.
Forty crabs are placed into each beaker containing the test compound solution.

1. Count deaths after 2 and 5 days.

In this test, the compound of Example 1 is highly effective against Ades agibuti. Very high mortality rates are obtained with compounds 1.19 and 1.22, for example (80 to 100). Cotton plants in a stand having a height of 100 ml are sprayed with an emulsified aqueous solution containing a concentration of 400 and 8110 ppm of each of the compounds to be tested.

After the spray coating has been applied, the cotton plant (MiL3 one stage Subodoptera littoralis (8podoptera11t)
The larvae of J. toralis) and (J. Heliothis virescens) are collected. The test is carried out at 24° C. and 60 m relative humidity. After 120 hours the percent mortality of the test harmful microorganisms is determined.

The compound of formula (■) is very effective in this test. Compounds 1.19, t22, and others exhibit high mortality (75 to 100 kills) and low toxicity to plants.Example B9Aphis craccivo
Pesticide microbial action against ra) The leguminous plants with grown roots are transplanted into containers containing 600 cc of soil and then 25 p of the compound to be tested.
Pour 50- of the solution containing 50 pm, 5 ppm and 1 ppm directly onto the soil.

After 24 hours, lice of the Abys crassivola species are collected on the part of the plant above the soil and then placed on the plant in order to protect the lice from any possible contact with the test substance, either directly or via the gas phase. Cover completely with the plastic cylinder. Mortality is counted 48 hours after the start of the study. 1 each! Two plants in two containers are used for each of the given concentrations of test substance. Testing at 25°C and 70% relative humidity
The compounds of Tables 1 to 4 carried out in Table 1 are very effective against Apis crassibora. For example, compound 1.1
0, 1.22 and others have mortality rates of 70 to 100.
urticae) 12 hours before the test for acaricidal action,
Phaseolus vulgaris
The plants are collected using some of the leaves collected by a cultured population of Tetranychus urticae. The mobile stage moving into the plant is sprayed by a chromatography atomizer with an emulsifier of the compound to be tested so that the spray mixture does not escape. The count of living and dead organisms is 2.
and after 7 days under a binocular microscope and the results are expressed as percentages. During the test period, the plants are kept in a greenhouse compartment at 25°C.

In this test, the compounds of Tables 1 to 4 have good acaricidal activity against Tetranychus urticae.

Among others, compound 1.19 is sufficiently effective against larvae, adults and eggs.

Claims (1)

[Claims] (Eleventh formula 1: [In the formula, X represents the bridge 9P: member -CH= or -N=, and Ar
represents a haphenyl group, diphenyl group, or naphthyl group; 1'L, @R, and R are each independently a hydrogen atom. Represents a nitro group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms, and R4 is unsubstituted or a carbon substituted with a halogen atom. Alkenyl group having 2 to 10 atoms; unsubstituted or substituted with halogen atoms and having 2 to 10 carbon atoms
or a C3 -C8 cycloalkyl group or an unsubstituted or halogen atom, a C1 -C4 alkyl group. a C1 -C4 alkoxy group, a phenyl group substituted by -CN or -CF1; or a C2 alkyl group which can be interrupted by an oxygen or sulfur atom and is unsubstituted or , or a halogen atom. phenyl group, -COO-C1-C4 alkyl group, -CO-C1-C4 alkyl group,
-GO-phenyl group, unsaturated or saturated 5- or 6- containing an oxygen radical 4 or a yellow atom as a non-carbon atom
1 carbon atom substituted by an atom or group consisting of a membered ring and in which each phenyl group is unsubstituted or substituted with one or more identical or different halogen atoms; It represents an alkyl chain having 1 to 12 carbon atoms, and R6 is an alkyl group having 1 to 10 carbon atoms, each of which is unsubstituted, or a halogen atom. represents a phenyl group or benzyl group substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -CN or -CF, and R6 and R7 are each independently hydrogen; Atomic 9 scale elementary number of atoms 1
an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an aromatic ring which is unsubstituted or a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a halogen atom having an unsubstituted aromatic ring;
represents a phenyl group or benzyl group substituted with 4 to 4 alkoxy groups, -CNt or -CF,
or one of R and R7 is -N(R8>(Re)4
'c also represents 5, or both together, and also contains one nitrogen atom with a size of 2.11 m1
A negative ~ or filtered, saturated oro or unsaturated heterocycle IJ song is formed, R8 and Ro are each independently a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted halogen atom, an alkyl group having 1 to 4 carbon atoms,
represents a phenyl group substituted with -CN or -CF3, Rlo represents an alkyl group having 1 to 12 carbon atoms, and RII represents an alkyl group having 1 to 12 carbon atoms or a phenyl group, In the formula, a+t represents an alkyl group having 1 to 12 carbon atoms, and Y represents an oxygen atom or a sulfur atom. ] Phosphoric esters and acid salts. Quaternary azolium and ammonium salts and their metal complexes. (2) The following formula 1*= [In the formula, Each independently represents a hydrogen atom, a nitro group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a haloalkyl group having 1 to 3 carbon atoms, and melon has 1 carbon atom. to 4 alkyl groups. Phenyl represents a phenyl group or benzyl group each substituted with one or more nitro groups, halogen atoms and/or methyl groups, and R3o represents an alkyl group having 1 to 6 carbon atoms. In the formula, RII represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, R'tt represents an alkyl group having 1 to 6 carbon atoms, and Y represents an oxygen atom or a weight atom. The compound according to claim 1 and the acid salt, quaternary azolium and ammonium salt, and metal complex thereof, which are suitable for agricultural use. (3) In the above formula 1, X is a bridge member - 〇H-or-
N= represents; Ar represents a phenyl group; 几 at the ortho-position is a hydrogen atom, a nitro group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon atom Represents a haloalkyl group of numbers 1 to 3; R2 at the para position is a hydrogen atom, and a nitro group. halogen atom, alkyl group having 1 to 3 carbon atoms, flukoxy group having 1 to 3 carbon atoms or 1 carbon atom
- represents a herooalkyl group: R8 is a hydrogen atom,
R6 represents an alkyl group, a phenyl group, or a phenyl group or a benzyl group each substituted with one or more nitro groups, a halogen atom, and/or a methyl group; R6 is an alkyl group having 1 to 10 carbon atoms; or each unsubstituted, or halogen atom, number of carbon atoms 1
an alkyl group having 1 to 4 carbon atoms, a rucoxo group having 1 to 4 carbon atoms; represents a phenyl group or a benzyl group substituted with -CN'l or -CF; each of R6 and R7 is independently a hydrogen atom, a C1-C3 alkyl group, a C3-C7 alkyl group; represents a cycloalkyl group, phenyl group or benzyl group; R1° represents an alkyl group having 1 to 4 carbon atoms; Rlj represents -Y1'L, 2e
The compound according to claim 1, wherein R72 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; and Y represents an oxygen atom or a sulfur atom; and Acid salts, quaternary azolium and ammonium salts and their metal complexes. (4) In the above formula 1, in the formula, X represents a bridge tool -N=; group: is a nitro group at the ortho position and/or para position. Fluorine atom, chlorine atom, bromine atom, methyl group. Represents a phenyl group substituted with a methoxy group and/or CF; R represents a group; represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a phenyl group or benzyl group each substituted with a nitro group, a chlorine atom, a bromine atom, a fluorine atom and/or a methyl group; R+o represents an alkyl group having 1 to 4 carbon atoms; 4 represents an alkyl group; R1 represents -YRI, I represents an alkyl group having 1 to 4 carbon atoms or a phenyl group; R1,
2. The compound and acid addition salts, quaternary azolium and ammonium salts, and metal complexes thereof according to claim 1, wherein Y represents an alkyl group having 1 to 4 carbon atoms; and Y represents an oxygen atom or a sulfur atom. (5) The compound represented by the above formula 1 is the following formula 1.3:
1. A compound according to claim 1, which represents a compound represented by: (6) The compound represented by the above formula I is the following formula 1.19:C
00C,H. A compound according to claim 1, which represents a compound represented by: (7) The compound according to claim 1, wherein the compound represented by the above formula 1 represents a compound represented by the following formula 1,22:. (8) The compound represented by the above formula I has the following formula 1.51:
A compound according to claim 1, which represents a compound represented by: (9) Copper compound according to claim 1. Metal complexes with zinc, magnesium or tin. αI With a suitable carrier, the following formula 1: [wherein, Atom, nitro group, halogen atom, alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 5 carbon atoms, or halogen having 1 to 3 carbon atoms are unsubstituted or substituted with a halogen atom. 2 to 10 alkenyl; unsubstituted or C2 to C10 alkynyl substituted by a halogen atom; or C3 to C8 cycloalkyl or unsubstituted or halogen, carbon atom alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl substituted by - or -CF; or alkyl of 2 carbon atoms interrupted by an oxygen atom or (jf yellow atom); and is unsubstituted or a halogen atom; phenyl, -COO-C1-C4alkyl, -CO-C1-C4alkyl, -
Co-phenyl group, consisting of an unsaturated or saturated 5- or 6-membered ring containing oxygen or sulfur atoms as non-carbon atoms, and each phenyl moiety is unsubstituted or has one or more identical or represents an alkyl chain having 1 to 12 carbon atoms substituted with an atom or group selected from the group substituted with a different halogen atom, and R1 is an alkyl group having 1 to 10 carbon atoms, or each is unsubstituted or , or a halogen atom. represents a phenyl group or benzyl group substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -CNI or -CF, and R6 and R7 are each independently a hydrogen atom; , number of carbon atoms: 1
an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an aromatic ring is unsubstituted or/) a rogene atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, represents a phenyl or benzyl group substituted by -CN or -CF, or one of R6 and R7 also represents a -N(Rs)(R,) group, or both together, and also one a 5- or 6-membered, saturated or unsaturated heterocyclic ring containing 1 or 2 nitrogen atoms, R8 and Ro are each independently a hydrogen atom, 1 carbon atom,
represents an unsubstituted or phenyl group substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, -CN or 10F, and R1° is an alkyl group having 1 to 12 carbon atoms; represents a group, and R1, is -YR,! , represents an alkyl group having 1 to 12 carbon atoms or a phenyl group, 几 represents an alkyl group having 1 to 12 carbon atoms, and Y represents an oxygen atom or a sulfur atom. A pesticidal microbial agent composition for suppressing or controlling infection of plants by microorganisms containing a phosphoric acid ester represented by the following formula, and at least one of acid-added LJIK g quaternary azolium and ammonium salts and their gold complexes. . (fil) The following formula I: H [wherein, hydrogen atom, nitro group, halogen atom, alkyl group having 1 to 3 carbon atoms,
C1-C3 alkoxy group or C1-C3 quince is unsubstituted or C2-C10 alkenyl group substituted with a halogen atom: unsubstituted or substituted with a halogen atom C2 -C10 alkynyl; or C6 -C8 cycloalkyl or unsubstituted or halogen, C1 -C4 alkyl. a phenyl group substituted by a C 1 -C 4 alkoxy group, -CN or 10F; or a C 2 alkyl group which can be interrupted by an oxygen or sulfur atom and is unsubstituted; or halogen atom, phenyl group, -■〇-C1-C4 alkyl group, -CO-C1-C4 alkyl group, -CO-phenyl group, oxygen atom as a non-carbon atom, or selected from the group consisting of an unsaturated or saturated 5- or 6-membered ring containing a sulfur atom, and in which each phenyl group is unsubstituted or substituted by one or more of the same or different halogen atoms; R5 represents an alkyl chain having 1 to 12 carbon atoms substituted with an atom or group having 1 to 10 carbon atoms, each of which is unsubstituted, or a halogen atom. represents a phenyl group or benzyl group substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -CN or -CF, and R6 and R7 are each independently a hydrogen atom, Number of carbon atoms: 1
an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an unsubstituted aromatic ring or a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, - represents a phenyl group or benzyl group substituted by CN or -CF,
or 5- or 6-membered, in which one also represents a -N(R4) (几, ) group, or both together further contain one or two nitrogen atoms;
Forming a saturated or unsaturated complex i1J, R8 and 几. are each independently hydrogen atom, carbon atom number 1
It represents an alkyl group having 1 to 4 carbon atoms, an unsubstituted phenyl group, or a phenyl group substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, -CN or -CF. ] and the following formula III: [wherein R1 represents an alkyl group having 1 to 12 carbon atoms, and R11 represents an alkyl group having 1 to 12 carbon atoms or a phenyl group] and an represents an alkyl group having 1 to 12 carbon atoms;
Further, Y represents an oxygen atom or a sulfur atom, and Hal represents a halogen atom. ] in the presence of an inorganic or organic filler, from −20° to +
The reaction is carried out in the temperature range of 150°C without a solvent or in the presence of an inert organic solvent or diluent and/or the free compound obtained in this step is converted into an acid salt or a quaternary azolium salt or an ammonium salt. converting into a salt, or converting the acid salt or quaternary zolium salt or ammonium salt obtained by this step into a free compound or other acid salt, quaternary azolium or ammonium salt;
or by converting the free compound or salt obtained by the process of the present invention into a metal complex according to the following formula ■: [wherein X e A r * R, s R2 * Rs@
R+ fLlo + 几1. and Y is of the above formulas II and I
It has the same meaning as defined in II. ] A method for producing a phosphoric acid ester, an acid salt, a quaternary azolium salt, an ammonium salt, and a metal complex thereof. The following formula I together with suitable solid and/or liquid carriers and/or surfactants:
represents a phenyl group, diphenyl group or naphthyl group, R1m'' and R3 each independently represent a hydrogen atom, a nitro group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or C1-C3 haR4 is an unsubstituted or halogen-substituted alkenyl group;
an unsubstituted alkynyl group having 2 to 10 carbon atoms, each substituted by a halogen atom; or a cycloalkyl group having 3 to 8 carbon atoms, or an unsubstituted halogen atom, having 1 to 4 carbon atoms; Alkyl group of. a C1 -C4 alkoxy group, a phenyl group substituted by -CN or -CF; or a C2 alkyl group which can be interrupted by an oxygen or sulfur atom and is unsubstituted; or/
X rogen atom, phenyl group, -COO-alkyl group having 1 to 4 carbon atoms, -CO-alkyl group having 1 to 4 carbon atoms M *-Co-phenyl group, containing oxygen or sulfur atom as a non-carbon atom unsaturated or saturated5
- or a 6-membered ring, and each phenyl group is unsubstituted or substituted with an atom or group selected from the group consisting of one or more of the same or different halogen atoms. It represents an alkyl chain having 1 to 12 atoms, and ``D'' represents an alkyl group having 1 to 10 carbon atoms, each of which is unsubstituted, or /X rogen atom. represents a phenyl group or benzyl group substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -CN or -CF, and R6 and R7 are each independently a hydrogen atom, Number of carbon atoms: 1
alkyl group having 3 to 6 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms;
Alkyl group or aromatic ring is unsubstituted or halogen atom, alkyl group having 1 to 4 carbon atoms, 1 carbon atom
to 4 alkoxy groups, -CN or -cF3 represent phenyl or benzyl groups, or one of R6 and R7 also represents -N(Rs)(R9), or both together And, on top of that, 1 more
forming a 5- or 6-membered, saturated or unsaturated complex i1J ring containing 1 or 2 nitrogen atoms;
and R, are each independently a hydrogen atom, a C1-C4 alkyl group, or an unsubstituted or halogen atom,
C1 -C4 alkyl group, -CN or -C
F, represents a phenyl group substituted with -R1° represents an alkyl group having 1 to 12 carbon atoms; , R8, represents an alkyl group having 1 to 12 carbon atoms, and Y represents an oxygen atom or a sulfur atom. A method for producing a noxious microbial composition, which comprises thoroughly mixing the compound represented by the following formula, and at least one of acid salts, quaternary esters, ammonium salts, and metal complexes thereof. α4 Formula I: [wherein, Nido a group, halogen atom, C1-C3 alkyl group, C1-C3 alkoxy primary or C1-3 a- is unsubstituted or carbon substituted with a halogen atom alkenyl group having 2 to 10 atoms;
an unsubstituted or halogen-substituted alkynyl group having 2 to 10 carbon atoms; or 3 carbon atoms;
-8 cycloalkyl group or unsubstituted or halogen atom, C1 -C4 alkyl group. a C1-C4 alkoxy group, a phenyl group substituted by -CN or 10F; or a C2 alkyl group which can be interrupted by an oxygen or sulfur atom and is unsubstituted; Is there or/
10 gen atoms, phenyl group, -COO- number of carbon atoms 1
alkyl group having 1 to 4 carbon atoms, -CO- having 1 to 4 carbon atoms
alkyl group, -CO-phenyl group, unsaturated or saturated 5 containing oxygen or sulfur atoms as non-carbon atoms
- or a 6-membered ring, and each phenyl group is unsubstituted or substituted with an atom or group selected from the group consisting of one or more of the same or different halogen atoms. It represents an alkyl chain having 1 to 12 atoms, and 几 is an alkyl group having 1 to 10 carbon atoms, or each is unsubstituted or a halogen atom. represents a phenyl group or benzyl group substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -CN or -CF, and R1 and R1 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an aromatic ring having an unsubstituted or substituted atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 1 to 4 carbon atoms; represents an alkoxy group, a phenyl group or a benzyl group substituted by -CN or -CF3, or one of R6 and Rρ also represents a -N(Rs)(R1) group, or both together, and furthermore form a 5- or 6-membered, saturated or unsaturated heterocyclic ring containing one or two nine-membered atoms, R8 and R, independently of each other, have a hydrogen atom, a carbon number of 1
represents an unsubstituted or phenyl group substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, -CN or 10F, and Rlo is an alkyl group having 1 to 12 carbon atoms; and R11 represents a C1-C12 alkyl group or a phenyl group, R1! represents a C1-C12 alkyl group, and Y represents an oxygen atom or a sulfur atom. A phosphoric acid ester, an acid, and an added salt represented by the following formula. for the control of pathogens, insects or mites, or for the protection of cultivated plants from attack by the above-mentioned harmful microorganisms.